TW201700703A - Sealing mass based on mercaptoterminated basis polymer/epoxid compound and process to harden by means of a photolatent catalyst - Google Patents

Abstract

The present invention relates to a sealing mass for coating a substrate, which is a mixture of a predominantly unhardened matrix and a hardener containing at least one epoxy compound, wherein the matrix contains a mercapto-terminated base polymer based on polyether, polythioether, polythioethersulfide, polysulfide, copolymers thereof and/or mixtures thereof, wherein the matrix, the hardener or both contain at least one photoinitiator based on a sterically hindered nitrogen-containing organic base, and, through the effects of energy-rich actinic radiation, the at least one photoinitiator dissociates at least one radical per molecule based on a nitrogen-containing organic base, from which a nitrogen-containing organic base having a pKs value of the conjugated acid in the region of 6 to 30 is formed, which acts as an active catalyst for the hardening of the matrix. The present invention also relates to a corresponding method for coating a substrate with a sealing compound.

Description

Sealing material for base polymer/epoxide compound based on thiol termination and method for hardening by photolatent catalyst

The present invention relates to a sealing material based on a thiol-terminated base polymer/epoxide compound and a method of hardening the sealing material on a substrate by a photolatent catalyst. In particular, the metal substrate or the coated metal substrate may be applied, but the substrate composed of other material groups may be coated. The sealing material is also used here to connect and/or bond (construct) the components and to seal and/or fill the cavities and/or intermediate cavities of the (construction) components.

This invention relates to a two component system consisting of a binder and a hardener.

The concept of "(unhardened) binder" is used hereinafter to mean a mixture that has not been incorporated into a hardener.

On the one hand, the concept of "sealing material" means a mixture of a binder and a hardener which, after being mixed with a hardener, is in an unhardened or hardened state and is ready for use (especially for coating substrates), and the other Aspect, this concept also means (for example, on the substrate) A hardened mixture of a material and a hardener.

Binders and sealing materials are used in a variety of different applications. It is mainly used in the aerospace and aerospace fields, but it is also suitable for any field where the amount of base material or sealing material is large and special emphasis is placed on rapid hardening, such as land vehicles. It is used in particular for sealing structural elements for, for example, slabs with existing constructions (for example segments of an aircraft) and/or for use in the area of drilling, where the corrosion protection layer of the metal component is damaged or Anti-corrosion is achieved on the removed parts. For example, in the course of transportation in the development of a permanent connection element for carrying the load, the base material and the sealing material can also temporarily assume the load-bearing function.

For the manufacture and maintenance of aircraft and spacecraft, special requirements are imposed on the base material and sealing material: (for example, fuel tank) seal, corrosion protection, aerodynamic smoothness of the pressure body (Druckrumpf), over a wide temperature range The internal elasticity, resistance to various media such as fuel, hydraulic fluid, condensed water and deicing fluid, as well as sealing and adhesion on various substrates are important factors.

At present, the manufacture and maintenance of aircraft and spacecraft containing a large number of joints with sealing materials is extremely complicated, because the sealing materials currently used, especially the sealing materials with long processing time, need to be extremely long. The time to achieve complete hardening.

A disadvantage of the conventional sealing materials and methods in handling and hardening is that the sealing material can be fed in a given processing time to be followed, so that the catalyst hardened with a desired degree of acceleration is too small. Especially in the case of a long processing time, this can lead to a serious delay in the working process due to its correspondingly long hardening time. However, in the case of a sealing material having a long processing time, rapid complete hardening is also required.

The basic polymerization method with a thiol termination is currently used for a treatment time of 30 minutes. The rapid hardening type sealing material of the compound reaches a Shore A hardness of 30 in about 180 minutes. This setting can only be achieved with a special sealing material composition.

Another problem is that when a two-component and preferably room-temperature hardening sealing material is used, the time for achieving the tack free time and the total hardening time are much longer than the processing time (see Table 1). Therefore, conventional coating methods are often associated with extremely long cycle times in the production process (see Table 2).

The time before the Shore A hardness of 30, determined according to ISO 7619-1 or ISO 868 (hardness tester method), can be used as a standard for the degree of hardening. Furthermore, the non-stick time is an important dimension for the hardening of the sealing material which begins on the surface of the sealing material. Therefore, the processing time should be as long as possible, and the non-stick time and the complete hardening time should be as short as possible. For these parameters, most of the processing time is the starting point, while the non-stick time and the complete hardening time are generally determined by the type of sealing material. Table 1 gives the definition of important time parameters in the hardening of the sealing material. Table 2 is a summary of typical times during the hardening of the sealing material in the case where the base polymer terminated in the prior art is compared with the present invention.

Table 2: Conventional sealing materials in the prior art (epoxy resin hardened polysulfide sealing material hardened at room temperature and manganese dioxide hardened polysulfide sealing material), and during hardening of the sealing material of the present invention Trends and a list of typical times of choice (for 巯基终

In addition, in the case of a treatment time of 30 minutes, the traditional sealing materials of Class A and Class B (usually used in the form of flat or strip-like sealing materials for coating bolts, rivets or other structural elements) are usually required It takes 1.5 to 5 hours to enter the non-stick state, and usually takes 2.5 to 8 hours to reach a Shore A hardness of 30. For the intermediate layer sealing material (type C), the extruded material can be hardened by UV light.

According to the present invention, it is possible to significantly shorten the non-stick time and the complete hardening time in a case where the processing time is sufficiently long, thereby significantly reducing the time consuming. This significantly shortens the time period of other applications in which the components of the sealing material are applied.

A problem with conventional high-priced two-component sealing materials based on sulfhydryl terminated base polymers is that relatively high levels of free catalyst are required to achieve complete hardening and short non-stick time quickly. Among them, the processing time of these sealing materials is shortened in proportion to the shortening of the non-sticking time.

In addition to or as an alternative to tensile shear strength, a Shore A hardness of at least 35 or even only 30 is generally used as a standard for the mechanical strength of a slowly hardening sealing material in hardening, wherein the sealing material no longer occurs Plastically deformed and, for example, will not be smoothed during transport. The typical Shore A hardness of a fully hardened sealing material is typically 45 +/- 10.

DE 101 08 136 A1 describes a fast-curing sealing material having a relatively long treatment time. Which uses temperature, IR radiation or mechanical force to trigger rapid hardening, and Seal or deactivate the catalyst to maximize processing time.

No. 3,645,816 describes a method for sealing a leak in a liquid storage tank, for example in the case of a polysulfide sealing material, wherein for accelerated hardening, the sealing material is heated to a temperature of 60 to 65 ° C for extremely fast implementation. It does not stick to time and harden, but this solution can only be applied to specific sealing materials. It is difficult to heat a substrate that is large or difficult to reach.

US 2013/0137817 A1 describes a polysulfide-based Cure on Demand sealing material. Where a closed hardener is used, the hardener is deblocked/activated at 60-120 ° C for up to 2 hours. Such higher activation temperatures and longer activation times are detrimental to substrates that are commonly used in aircraft manufacturing, such as aluminum alloy substrates, because of the higher coefficient of thermal expansion of such substrates.

UV-curable one-component or two-component room temperature hardening coatings are known, which do not have sulfur-containing polymers and do not exhibit particularly advanced properties of aircraft sealing materials, such as for fuels, hydraulics High resistance to liquids, condensate and de-icing fluids. These coatings are generally based on a UV-curable mixture comprising a double bond acrylate prepolymer which is capable of free radical polymerization and hardening as a free radical generator in the presence of a photoinitiator. However, in the case of such sealing materials, complete hardening cannot be achieved without UV radiation.

One of the unfulfilled expectations of the development of binders and sealing materials since the decades has been: to propose a binder and sealing material that achieves, for example, at least 0.5 hours, at least 1 at room temperature or slightly above room temperature. Hours or even about 2 hours of processing time, and it is not necessary to make the total hardening time several times this time. Another long-felt unfulfilled desire is to propose a binder and sealing material that begins to harden in accordance with the instructions.

It is an object of the present invention to provide a binder and a sealing material, and a method of coating a substrate by a sealing material comprising a thiol terminated polymer, wherein the hardening time is as short as possible while maintaining a long processing time. For use in aerospace and aerospace applications, the sealing material should have as much advanced properties as possible for conventional sealing materials used for this purpose. These characteristics include high resistance to various media, such as fuel resistance at room temperature, 60 ° C and 100 ° C, resistance to hydraulic fluid, condensed water, deicing fluid, high heat resistance, higher Low temperature flexibility, high weatherability, high peel strength for different substrates, high elongation at break and high tensile strength.

Another object of the present invention is to provide a binder and sealing material, particularly for use in the aerospace industry, which begins to harden as "in accordance with the instructions". In the absence of an instruction, the sealing material preferably still completely hardens, albeit with a delay.

The following solutions are currently found to be feasible: manufacturing base materials and sealing materials that can be hardened according to the instructions. At present, it has also been found that the following schemes are feasible: the base material and the sealing material having a very short non-stick time after being irradiated with high-energy actinic radiation, and the complete hardening time can be substantially in the order of processing time (refer to Table 2 above). In the aircraft manufacturing process, the waiting time and cycle time can be shortened, thereby increasing productivity. It has also been found that these base materials and sealing materials have substantially the same advanced properties as conventional base materials and sealing materials used in the aerospace and aerospace industries, particularly high fuel resistance and high elasticity.

The sealing material system of the invention also has the advantage of achieving hardening in the unirradiated area of the sealing material, the so-called "blind zone", and achieving subsequent hardening, so that even if the irradiation time is too short and/or the sealing material is applied In the case where the irradiation in the layer region is incomplete, complete hardening can still be achieved.

The method of the present invention is characterized in that the sealing material is hardened in accordance with the instructions, and the hardening is so fast that the non-stick surface of the sealing material is achieved within a non-sticking time of <15 minutes from the start of the irradiation. In a preferred embodiment, the sealing material begins to harden with the onset of high energy actinic radiation. The non-stick time is preferably <10 minutes, <5 minutes, <3 minutes or <10 seconds. The complete hardening time achieved therein is from 1 to 1000 minutes, preferably from 1 to 360 minutes, and more preferably from 20 to 90 minutes, depending on the thickness of the layer.

Therefore, the base material and sealing material of the present invention are a new type of sealing material which is particularly suitable for use in aircraft, has a relatively long processing time, begins to harden according to the command, and the hardening speed is greatly increased. Because these materials are particularly fast to enter the non-stick state.

The solution of the present invention for achieving the above object is a sealing material for coating a substrate, which is a hardened base material (ie, a base having a viscosity of <2500 Pa.s) and a hardening compound containing at least one epoxide compound. A mixture of agents comprising a thiol-terminated base polymer based on a polyether, a polysulfide, a polysulfide sulfide, a copolymer thereof, and/or a mixture thereof, the binder, the hardener, or both a photoinitiator comprising at least one sterically hindered nitrogen-containing organic base, and the at least one photoinitiator separates at least one free radical based on the nitrogen-containing organic base for each molecule under the action of high-energy actinic radiation This constitutes a nitrogen-containing organic base having a pKs value of 6 to 30 as a conjugate acid, which is used as an activation catalyst for hardening of the binder.

The conjugated acid of the nitrogen-containing organic base used as the activated catalyst for hardening of the binder preferably has a pKs value of from 7 to 28, further preferably from 8 to 26, particularly preferably from 9 to 20, most preferably from 10 to 15. .

The at least one sterically hindered nitrogen-containing organic base-based photoinitiator is preferably a sterically hindered tertiary amine, a hindered ruthenium and/or a sterically hindered ruthenium. Correspondingly, the at least one photoinitiator is in high energy photochemical At least one free radical based on tertiary amine, hydrazine and/or hydrazine is separated for each molecule by the action of radiation.

The present invention also relates to a method of coating a substrate with the sealing material, wherein the substrate is coated with the sealing material, the sealing material is irradiated with high-energy actinic radiation, and then the sealing material is hardened.

There is also a method of joining elements, sealing and/or filling the cavity and/or intermediate cavity of the element, and making a hardened sealing material. The component therein refers in particular to the structural component.

The viscosity of the binder and sealing material can also be so small that the binder and sealing material can be ejected onto the substrate by suitable equipment.

Higher temperatures are required to activate the photoinitiator of the present invention, or the catalyst thus constructed is used as a catalyst, and only high energy actinic radiation, such as UV light, is required.

Another advantage of the present invention is that hardening can be achieved at room temperature or only slightly above room temperature, for example at temperatures of 10 to 40 or 15 to 30 °C.

Under the action of high-energy actinic radiation, at least one photoinitiator employed in the present invention separates at least one free radical based on a nitrogen-containing organic base for each molecule, in particular through H absorption (for example in the case of tertiary amines) And/or H is released (for example in the case of hydrazine), and in particular as a catalyst for hardening. Preferably, the photoinitiator releases and/or constitutes a tertiary amine, hydrazine and/or hydrazine under the action of high-energy actinic radiation, and the released and/or composed amine, hydrazine or hydrazine terminates in the thiol group. The base polymer is catalyzed by a reaction between the epoxide-based hardener. More preferably, the photoinitiator triggers and/or accelerates the reaction of the epoxide compound with the mercaptan in the event that the encapsulant is exposed to high energy actinic radiation.

It has also been found that sulfhydryl terminated base polymers can be used in the following cases. And a suitable additive to produce a sealing material that is rapidly hardened according to the instructions and has advanced properties: epoxide hardening is selected, and a preferred amount of photoinitiator is added, which is based on tertiary amines and/or hydrazine under high-energy actinic radiation. / or 胍 releasing at least one free radical for each molecule, wherein the ratio of the tertiary amine and / or hydrazine and / or hydrazine compound to the total composition of the sealing material of the invention is 0.05 to 5 wt% or 0.1 to 4 wt% or 1 Up to 3 wt%, or, for every 100 g of the base, constitutes from 0.2 to 23 mmol or from 0.45 to 18.3 mmol or from 4.5 to 14 mmol of tertiary amine and/or hydrazine and/or hydrazine compound. This ratio of tertiary amine or ruthenium or osmium is clearly sufficient as a catalyst to harden a layer, strip or ridge of sealing material, for example about 7 mm thick.

In the case where high energy actinic radiation acts on the sealing material and/or the hardening sealing material, at least one photoinitiator releases at least one tertiary amine and/or hydrazine for each molecule during its separation. And/or free radicals. Here, the photoinitiator is not used for radical sclerosis such as acrylates and/or methacrylates as usual, but as a "base polymer" for triggering the termination of epoxide compounds and sulfhydryl groups (selected from The form of the polymer and/or copolymer) is an addition polymerization reaction. Because acrylates and methacrylates and other organic polymer systems of the prior art have a large number of double bonds, there is generally no double bond for the base polymer terminated in this case. In addition, benzamidine radicals are mainly or only required in the hardening of (meth) acrylate, and tertiary amines or free radicals composed of tertiary amine radicals are required in the hardening of the thiol-terminated base polymer. The composition of the base or the composition of the free radicals, and the benzamidine radicals are required in the process of the invention.

As far as the applicant of the present invention is concerned, with the methods of the prior art, it is not possible to effect free radical polymerization through a photoinitiator without a compound or group having a double bond. However, such a double-bonded component is usually not added to the base material and the sealing material of the present invention, so as far as the applicant knows, Free radical hardening will occur.

The chemical composition of many UV-curable coatings in the prior art is based on acrylates, the cross-linking of which is triggered by the illumination of UV light, especially in the presence of a photoinitiator. However, in the case of a large layer thickness, the UV light can only locally enter such a coating, so in practice it is not possible to achieve hardening for a layer thickness of, for example, more than 200 μm.

The present invention is based on the use of a reaction of an epoxy group with a fluorenyl group in the presence of a tertiary amine and/or hydrazine and/or hydrazine as a catalyst for the reaction. Wherein, even if the layer thickness of the sealing material is much larger than 200 μm, a complete reaction can be achieved, and for example, a layer thickness of about 7 mm can be hardened because the photoinitiator releases and converts to catalytically activated amine and/or hydrazine and/or The amine or hydrazine or hydrazine of the hydrazine can obviously be distributed over a large distance throughout the sealing material. Further, by using another free catalyst, it is preferably a free nitrogen-containing organic base having a pKs value of 6 to 30, preferably a free tertiary amine and/or free ruthenium and/or free. Oh, it is possible to achieve rapid deep hardening in the sealing material as in conventional sealing materials.

Wherein "deep hardening" refers to a hardening reaction that is not triggered by direct UV light on the surface of the UV-curable sealing material, but occurs a few millimeters below the surface of the sealing material. Deep hardening depends on the choice of filler and other additives that affect, for example, the color of the sealing material. Surface hardening usually occurs within 2 mm, and deep hardening is performed below it.

UV light cannot be incident directly at this depth, so another free catalyst is used which assists in this deep hardening. The treatment time and the complete hardening time can be adjusted depending on the application, depending on the choice of free catalyst.

The present invention relates to chemical hardening in which the photoinitiator of the present invention is used for other purposes, and is generally only used to release amine radicals and/or purine free radicals and/or purine free radicals to constitute a basis for A tertiary amine or a catalyst of ruthenium or osmium, and is not used as a photoinitiator in the original sense.

Preferably, no or almost no heat is input from the outside into the chemical system, but the following scheme is adopted: the sealing material is mainly or completely in a temperature range of 10 to 40 ° C or 15 to 30 ° C from the action of high-energy actinic radiation. hardening. Temperatures above 40 ° C are rarely provided or produced in the process of the invention. An advantage of the method of the present invention is that a higher temperature is required. In addition, temperatures above 80 °C may cause stress in the component due to thermal expansion and may have a negative impact on adjacent components such as aluminum alloys and fiber composites. Even if this is the case, it is usually based solely on actinic radiation and possibly exothermic chemical reactions, and is only heated to over 40 ° C or even over 60 ° C for a time range of about 1 to 15 minutes. The hardening is preferably carried out at a temperature ranging from 10 to 40 ° C and from 15 to 30 ° C, wherein in individual cases, temperatures in excess of 40 ° C or even 50 ° C are also employed in a time range of only 0.1 to 15 minutes. More preferably, the hardening is carried out in the range of 15 to 30 ° C at all times. More preferably, the hardening is carried out at a temperature below 30 ° C in most or all of the time.

The binder or sealing material of the invention preferably has at least one photoinitiator based on at least one of the hindered tertiary amine groups and/or the oxime group and/or the oxime group. The photoinitiators of the present invention can have different configurations.

Unlike conventional sealing material systems which are hardened with isocyanates or vinyl compounds, the systems newly described herein are generally not supported by, for example, acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, 2,4,6-trimethylbenzylidene-diphenylphosphine oxide, 2-dimethylamino-2-(4-methyl-benzyl)-1 -(4-4 morpholinyl-phenyl)-butan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinyl)-1-butanone catalyst .

The alkalinity of these catalysts is too weak. Therefore, the photoinitiator used in the present invention is Light-potential strong basic nitrogen compounds. Accordingly, the released conjugated acid of the nitrogen-containing organic base has a pKs value of from 6 to 30, preferably from 7 to 28, further preferably from 8 to 26, particularly preferably from 9 to 20, most preferably from 10 to 15. . Preferably, the photoinitiator is selected from the group consisting of sterically hindered amines and/or ruthenium and/or osmium photoinitiators which release and/or produce tertiary amines and/or hydrazine and/or under the action of high energy actinic radiation. guanidine. Preferably, a photoinitiator is used which separates 1, 2 or 3 tertiary amine radicals or purine free radicals or purine free radicals under high-energy actinic illumination, and/or which comprises at least one for each molecule a compound of 2 or 3 tertiary amine groups or a hydrazine group or a hydrazine group.

The photoinitiator of the present invention is optionally a latent catalyst in which only the activated catalyst is released or formed. However, depending on the circumstances, such photoinitiators can also have minimal catalytic effects prior to high energy actinic radiation.

The photoinitiator of the invention preferably belongs to the class of hydrazine and/or tertiary amines and/or hydrazine. Because the chemical structure of such photoinitiators allows the release of ruthenium free radicals and/or amine free radicals and/or ruthenium free radicals after high-energy actinic radiation, and constitutes ruthenium and/or tertiary amines and/or ruthenium, which The reaction between the thiol terminated base polymer and the epoxide-based hardener begins and/or accelerates. Thus, after the two components are mixed, the irradiation time of the sealing material of the present invention is generally ensured to be 15 minutes to 4 hours, preferably 20 minutes to 2 hours, or 30, without irradiation with high-energy actinic radiation. Minutes to 1 hour. In the case where the sealing material and its starting material are not subjected to sharp hardening during the manufacturing and storage time, the sealing material is an uncured mixture.

In the case where the binder or sealing material is exposed to high-energy actinic radiation, this operation achieves "hardening according to the instructions", extremely fast surface hardening (which is given by the non-stick time) and rapid complete hardening. First, a non-stick layer is formed on the outside, followed by intensive rapid hardening. It usually achieves a non-stick time of 0.01 to 5 minutes and complete hardening of 1 to 1000 minutes. Time, depending on the thickness of the layer. Among them, in the case of a sealing material to be transmitted to a thickness of 1 mm, a non-stick time of 0 to 5 minutes and a complete hardening time of 1 to 30 minutes are usually achieved. Among them, in the case of a sealing material to be transmitted to a thickness of 4 mm, a non-stick time of 0 to 5 minutes and a complete hardening time of 10 to 120 minutes are usually achieved. Among them, in the case of a sealing material to be transmitted to a thickness of 7 mm, a non-sticking time of 0 to 5 minutes and a complete hardening time of 20 to 240 minutes are usually achieved.

The photoinitiator can be used as a component of the binder and/or the hardener. Therefore, the photoinitiator is also a component of the sealant that can be used. The photoinitiator is preferably used as a latent catalyst which provides a tertiary amine and/or ruthenium and/or osmium for use as a catalyst.

According to a preferred embodiment, at least one photoinitiator is a sterically hindered quinone-based compound, preferably a photolatent 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, see Chemical formula I) and/or photolatent 1,5-diazabicyclo[4.3.0]non-5-ene (DBN, see formula II). As a sterically hindered compound, a nitrogen atom double-bonded in the free oxime carries a substituent R. This substituent R can have a different configuration. It may, for example, comprise an alkyl group or a phenyl group. Combinations of various organic residues may be employed in the substituent R in the form of short or long chain, branched or straight chain.

When the sterically hindered compound is exposed to high-energy actinic radiation, the ruthenium radical and the radical composed of the substituent R are decomposed. The ruthenium radical then absorbs the H atom and converts it into a reactive ruthenium.

Further, a photoinitiator based on a sterically hindered tertiary amine is preferably used. Suitable place The hindered amine can be, for example, based on triethylenediamine (1,4-diazabicyclo[2.2.2]octane).

Further, a sterically hindered ruthenium-based photoinitiator is preferably used. Suitable sterically hindered hydrazines can be based, for example, on closed photolatent TMG (tetramethyl hydrazine).

It is extremely important that the tertiary amine, ruthenium and osmium which are released after irradiation with UV light are strong bases, and the conjugate acid has a pKs value of from 6 to 30, preferably from 7 to 28, further preferably 8 to 26, particularly preferably 9 to 20, and most preferably 10 to 15. The corresponding sterically hindered compound has a much lower pKs value, preferably <9.5, prior to irradiation with UV light.

The tertiary amines, hydrazines and hydrazines are used herein as catalysts, and the released substituents generally do not cause interference in the thiol terminated polymer systems, but do not exert a positive effect. Hydrogen can be absorbed into the free radicals, for example, by the hydrogen groups of the self-presenting polymer and/or other organic compounds present. These constituent tertiary amines or ruthenium or osmium are generally more basic than the photoinitiator and are apparently useful as catalysts. In principle, the higher basicity of the newly formed tertiary amine and/or hydrazine and/or hydrazine relative to the photoinitiator can be measured by the pKs value of the corresponding conjugate acid. The advantage of higher alkalinity and/or the effect is that the reaction between the thiol and the epoxide compound is accelerated and the sealing material hardens very rapidly.

According to the prior art, the last mentioned photoinitiator is used in an acrylate-based UV-curable coating. In the present invention, the photoinitiator also surprisingly triggers the reaction of the epoxide compound with the thiol and/or accelerates the exposure of the sealing material to high-energy actinic radiation such as UV light. reaction. It has been surprisingly found that a photoinitiator that releases a relatively small amount of tertiary amine free radicals and/or hydrazine free radicals provides a sufficient amount of catalytically active tertiary amine or hydrazine compound for the hardening of the binder.

Wherein the photoinitiator is preferably a light latent DBN and/or a light latent DBU, as appropriate There is at least one photosensitizer such as benzophenone and/or thioxanthone. These photolatent bases release a much higher strength base than many other photoinitiators, thereby catalyzing the reaction between the thiol group and the epoxy group very efficiently.

In addition, an extremely efficient deep hardening of the sealing material is achieved by at least one photolatent, ie, sterically hindered tertiary amine and/or hydrazine and/or hydrazine (preferably DBN and/or DBU) and at least one Non-photoactive, ie free tertiary amine and / or hydrazine and / or hydrazine (preferably N-methylmorpholine, 1,4-dimethylpiperazine, 2,2'-dimorpholinyl di A combination of ethyl ether, tris(dimethylaminomethyl-phenol), triethylenediamine and/or TMG, and more preferably triethylenediamine and/or TMG) is used as the photoinitiator.

A photosensitizer can also be used. In principle, any photosensitizer which satisfies the following conditions can be used which shifts the absorption spectrum in the desired wavelength range, in particular in the UV-A range. Because the UV-A range is particularly suitable for larger layer thicknesses, and UV-A radiation does not form ozone. These photosensitizers shift the absorption spectrum, for example, from the short-wave UV range of UV-C 200-280 nm and/or UV-B 280-315 nm to the long-wave UV range of UV-A 315-380 nm compared to photoinitiators.

Therefore, it is preferred to use a mixture of a photosensitizer and a photoinitiator to specifically adjust the absorption wavelength of the binder or sealing material by at least one photosensitizer. The photosensitizer employed is preferably a photoinitiator that does not release tertiary amines and ruthenium or osmium, but it helps to adjust the absorption wavelength in a manner suitable for the particular application. To this end, exemplary mixtures are, for example, selected from the group consisting of: at least one photosensitizer (selected from benzophenone and isopropyl thioxanthone ITX), and at least one sterically hindered tertiary amine (eg, three-stranded ethylene) Amines and/or photoinitiators based on sterically hindered ruthenium (eg TMG) and/or sterically hindered ruthenium (eg DBN and/or DBU).

Hardening by chemical reaction of a thiol group with an epoxy group, wherein at least one is formed Hydroxy sulfide, hydroxy sulfide sulfide and/or hydroxy sulfide. Based on the free radical separation of the photoinitiator, no steric hindrance is required. A catalyst which is effective from the absorption of H (in the case of a tertiary amine) or evolved (in the case of hydrazine), which has a higher basicity and is no longer sterically hindered.

In the method of the present invention, the photoinitiator is not used to release free radicals as in the case of free radical UV hardening, but only amines and/or hydrazine and/or hydrazine are produced, which are accompanied by the formation of free radicals without hardening The process has an impact. The released tertiary amine radical or hydrazine radical or hydrazine radical is thereby absorbed or released by hydrogen (in the case of special measures) to constitute a tertiary amine or hydrazine or hydrazine, which is used here for chemical hardening. The catalytic reaction and/or catalytic acceleration of the chemical reaction between the epoxy group and the thiol group is carried out. The tertiary amine or ruthenium or osmium formed triggers the reaction between the base and the components of the hardener and/or accelerates it. The tertiary amine or ruthenium or osmium of this composition can obviously be used as a catalyst for the hardening of at least one epoxide compound at lower and higher temperatures. Among them, the photoinitiator functions as a latent catalyst. After separating the amine radical or hydrazine radical or hydrazine radical by the photoinitiator, after constituting the amine compound or hydrazine compound or hydrazine compound, and after catalysis of the hardening process, the amine or hydrazine or hydrazine continues It is in a free state and continues to catalyze after the end of the high-energy actinic irradiation, so that even subsequent hardening of the catalyst is usually achieved. During the subsequent hardening of the catalysis, the sealing material continues to harden even after the end of the high energy irradiation. This approach is obviously unique compared to the hardening based on the acrylate-based composition.

The latent catalyst triggers and/or accelerates the chemical reaction between the base polymer and the hardener under the action of high energy actinic radiation. In this way, the hardening can begin according to the instruction ("on demand"). This command is achieved by the high energy actinic illumination, for example with UV radiation. This gives the point in time at which the hardening begins and the start of the hardening.

In principle, actinic radiation, such as UV irradiation, can be carried out in 1 second to 6 hours. Irradiation is preferably carried out depending on the layer thickness and/or depending on the radiation source over a period of from 1 second to 15 minutes, although in principle a longer irradiation time can also be used. In the case of radiation doses of at least 1 J/cm ² , photochemical illumination of 5 seconds to 2 minutes is usually sufficient. If a UV-LED lamp emitting a wavelength of 365 nm is used, it is preferred to use a radiation dose of 1 to 20 J/cm ² at an intensity of 0.05 to 1.5 W/cm ² , particularly preferably at a strength of 0.2 to ^1.2 W/cm ² . using a radiation dose of 3 to 16J / cm ² in. If a UV-LED lamp emitting a wavelength of 395 nm is used, it is preferred to use a radiation dose of 3 to 20 J/cm ² at an intensity of 0.05 to 1.5 W/cm ² , particularly preferably at a strength of 0.1 to ^1.2 W/cm ² . A radiation dose of 6 to 17 J/cm ² is used. If a mercury lamp emitting a spectrum of a different wavelength is used, it is preferred to use a radiation dose of 1 to 25 J/cm ² at an intensity of 0.10 to 1.5 W/cm ² , and particularly preferably a strength of 0.2 to 1.0 W/cm ² . Radiation dose up to 20 J/cm ² .

Table 3 below again shows the above correlation of the wavelengths, radiation intensities and radiation doses employed.

In many embodiments, catalytic subsequent hardening, which typically lasts for hours or days, is achieved after irradiation, but also without prior illumination with high energy actinic radiation. According to a particular embodiment, this catalyzed subsequent hardening can be promoted by another non-sterically hindered catalyst. Thereby, this catalytic subsequent hardening can ensure that the sealing material is in use, especially in difficult or unusable At the portion of the radiation, a high quality is always achieved regardless of whether or not the activated catalyst is formed, and the position and composition thereof are formed.

In particular, UV radiation can be used as high energy actinic radiation, but as an alternative or in addition, electron radiation can also be used. The reliability of these types of radiation has been demonstrated because it includes the energy regions required to activate the photoinitiator, particularly UV light comprising UVC radiation, UVB radiation, UVA radiation and/or UV/VIS radiation. Thus, at least one UV radiator can be used, for example at least one high-efficiency UV radiator with a power of preferably more than 400 W, at least one low-power UV radiator with a power of less than 120 W, and/or at least one UV-LED, at least one for UV. A fluorescent radiant radiator, and/or at least one electronic radiator. If working in the UV-A range, no ozone is produced and a greater layer thickness (e.g., about 2 to 7 mm) hardening can be achieved.

For the sake of simplicity, only UV light or UV radiation is generally referred to below, and it is not limited to these wavelengths. However, UV light is most often used in practice.

The reaction of the present invention is greatly accelerated compared to conventional sealing materials which do not have high energy actinic radiation and which do not have such catalytic reactions. Reaction triggering by high-energy radiation is identifiable through extremely fast, possibly seconds, surface hardening. The acceleration of the reaction can be identified by accelerated hardening.

When the method of the present invention is used, the sealing material may have a Shore A hardness of at least 10, and/or may be performed 2 weeks after the start of high-energy actinic irradiation, according to measurements performed after 5 to 600 minutes from the start of high-energy actinic irradiation. The sealing material may have a Shore A hardness of 30 to 60. This significant increase in hardness is also attributed to this subsequent hardening until complete hardening. Among them, the speed can be controlled according to the photoinitiator and the content of free tertiary amine or free hydrazine or free hydrazine: the higher the content, the faster the hardening.

The invention has surprisingly found that a greater layer thickness can also be achieved by the sealing material system of the invention. Since a very small amount of the catalyst, in particular the tertiary amine and/or hydrazine and/or hydrazine, has caused the epoxide-thiol reaction to be greatly accelerated, a small amount is used to release the amine radical or the hydrazine radical or the hydrazine radical and It is also sufficient to form the corresponding amine or hydrazine or hydrazine trace component.

In this case, the chemical composition of the binder and the chemical composition of the curable sealing material can be selected such that the high-energy actinic radiation, such as UV light, is only absorbed to a lesser extent. The main component of the binder or sealing material is generally well permeable to high energy actinic radiation. In particular, in the case of fillers, it is preferred to ensure that they are excellently transmitted by the selected radiation. The ability of an electron beam to penetrate a substance of a binder or sealing material is generally much higher than UV light. Accordingly, when fillers and other additives are added to one of the materials, it is preferred to select such fillers and other additives: in particular, little or no absorption of the selected UV light type, or little or no absorption of the UV light. That is, it has as high a permeability as possible for the type of radiation selected to cause hardening. Preferably, the filler and other additives are absorbed in the UV spectrum or the range of UV light used for illumination. Fillers are typically added to the sealing material to improve mechanical properties. In particular, for the filler based on calcium carbonate and micro hollow spheres composed of glass or plastic, the beam permeability should be checked as needed.

Accordingly, it is preferred that no or only up to 1% by weight or only up to 5% by weight of a material, such as a filler, is added to the binder and the hardener: it absorbs significantly within the range of high-energy actinic radiation to be employed, or It absorbs absorption much higher than the sulfur-containing polymer of the binder.

Another great advantage of the invention is that after the start of the hardening, reliable and complete hardening is achieved without UV light, even after a long time (for example in 1) After 21 days, the hardening is achieved. This is important for applications where the sealing material is fed into the cavity and/or the gap between the components, and/or the sealing material is otherwise shielded from UV light, for example. Especially in the manufacture of aircraft, it is important that in any application the entire hardener-containing base fed is hardened as completely as possible.

The binder or sealing material of the present invention contains at least one sulfur-containing thiol-terminated base polymer based on a polyether, a polysulfide, a polysulfide, a copolymer as described above and/or a mixture thereof.

More preferably, the binder is based on a polythioether containing a terminal sulfhydryl group, and optionally a polysulfide containing a terminal sulfhydryl group.

According to a preferred embodiment, the binder is based on at least one liquid polysulfide compound having a thiol group at its molecular end. Wherein, the polythioether may optionally contain up to about 50 mol-% of a disulfide group in the molecule. It can also be called polysulfide sulfide. WO 2015/014876 A2 describes preferred such compounds having the following construction.

x=1.0-1.5

R = -(CH ₂ ) _p -O-(CH ₂ ) _q -O-(CH ₂ ) _r -, in addition, 0-20% of the R groups may carry a branched alkanediyl or argon diyl group .

n=1-60

q,p,r=1-10

According to another preferred embodiment, in addition to the at least one liquid polythioether compound, the binder contains at least one disulfide-containing compound, for example, at least one proportion of the binder More than 80% by weight of polysulfide.

In the composition of the base material of the present invention and the sealing material produced thereby, it is preferred to use a molecular weight of, in particular, 500 to 6000 g/mol, and particularly preferably a liquid polymer having a molecular weight of 900 to 5000 g/mol as a thiol-terminated polymer. Thioether polymer and / or polysulfide sulfide polymer. These thiol-terminated polythioether polymers and/or polythioether sulfide polymers may be single-branched or multi-branched molecules.

In the composition of the sealing material of the base materials thus produced of the present invention, the preferred molecular weight of a long chain polymer especially 2500 to 6000g / mol, as Thioplast ^® G13, plus a molecular weight of 3300 to 5000g / mol of long chain polymers, such as ^{Thioplast ® G10, Thioplast ® G12,} Thioplast ® G1, Thiokol ® LP 32 and / or Thiokol ^® LP 12 as mercapto-terminated polysulfide polymers. These thiol-terminated polysulfide polymers can also be single-branched or multi-branched molecules.

In the composition of the base material, the sealing material and the sealing material produced therefrom, the molecular weight is, in particular, additionally from 500 to 2500 g/mol, particularly preferably from 700 to 2000 g/mol, the optimum molecular weight of 800 to 1200g / mol of the short-chain polymers such as ^{Thiokol ® LP3, Thioplast ® G4,} Thioplast ® G22 or Thioplast ^® G44 as mercapto-terminated polysulfide polymers.

According to a preferred embodiment, in the composition of the base material, the sealing material and the sealing material produced therefrom, the molecular weight is particularly preferably from 2,500 to 6,000 g/mol, particularly preferably from 3,300 to 5,000 g/mol. Long-chain polymers, on the other hand, use short-chain polymers having a molecular weight of, in particular, from 500 to 2500 g/mol, particularly preferably from 800 to 1500 g/mol, as sulfhydryl-terminated polysulfide polymers and/or thiol-terminated poly-polymers. Sulfide and/or mercapto terminated polysulfide sulfide And wherein the ratio of the long chain polymer to the short chain polymer is preferably from 25:1 to 0.5:1, from 20:1 to 2:1, or from 14:1 to 8:1.

In the composition of the base material of the invention and the sealing material produced thereby, it is preferred to have a molecular weight of, in particular, from 100 to 7000 g/mol or from 500 to 6000 g/mol, more preferably a liquid polymer having a molecular weight of from 1000 to 3000 g/mol. The polyether polymer used as a thiol termination is also present in the sealing material thus produced.

The molecular weight can be determined by GPC (gel permeation chromatography) for polystyrene standards and/or polyethylene standards. Wherein, in a plurality of columns sequentially connected and filled with a porous material, the molecules of the polymer sample are separated according to the molecular weight, and for example by a refractive index detector, a viscosity detector and/or a light scattering detector It is identified. For example, THF (tetrahydrofuran) can be used as the mobile phase.

However, the molecular weight can also be determined by NMR spectroscopy (nuclear magnetic resonance spectroscopy).

The thiol content of the reactive SH groups of the sulfur-containing base polymer relative to the entire base polymer is from 0.5 to 10% by weight, from 0.8 to 8% by weight, or from 1.2 to 7% by weight.

Wherein, the thiol content of the polymers can be determined by direct titration of the SH terminated polymers with an iodine solution. To this end, the polymers were dissolved in a solvent mixture consisting of 40 Vol.-% pyridine and 60 Vol.-% benzene, and titrated with a phenyl iodide solution with stirring until a pale yellow color was present.

The total sulfur content of the sulfur-containing base polymers is preferably from 1 to 50% by weight, from 5 to 45% by weight or from 12 to 36% by weight.

As the reactive end group of the thiol group of each molecule, the average functionality of the sulfur-containing base polymers is preferably from 1.5 to 2.5 or from 1.9 to 2.2.

This functionality gives the average number of sulfhydryl groups per molecule. It was calculated as the quotient of the molecular weight: equivalent, and determined by NMR.

The average glass transition temperature T _g of the sulfur-containing base polymers is -80 to -30 ° C or -60 to -40 ° C, according to AITM 1-0003 (Airbus Industrial Measurement Method, June 1995) Measured.

The increased sulfur content can improve fuel resistance. In addition to the thiol terminated polymer/copolymer, the base polymer and/or the composition comprising the corresponding base polymer, such as the base material and/or the sealing material, may optionally contain from 0 or 0.001 to 10 or from 0.01 to 5% by weight. Oligomers, in particular selected from short-chain organic sulfides and/or short-chain organic thioethers. These short chain molecules contribute to the crosslinking and/or viscosity changes of the base polymer.

The composition of the present invention is either a binder in which the hardener is required to be used, or a one-component sealing material in which the binder is mixed with a hardener, preferably at least for a longer storage time. The composition of the components is frozen. The sealing material system or the main component of the composition is a system of at least two components consisting of an uncured binder and an epoxide-based hardener, and the principal component is produced by mixing One-component sealing material or sealing material. Here, all of the binder or sealing material contains at least one type of thiol terminated base polymer. Preferably, the binder or sealing material comprises at least one polysulfide-based sulfhydryl terminated base polymer, a polythioether-based sulfhydryl terminated base polymer, and/or a polythioether sulfide based sulfhydryl termination base The polymer, and/or the sulfhydryl-terminated base polymer based on polysulfide and polysulfide, may also be a polymer mixture and/or a copolymer, such as a block copolymer. The sealing material system, the uncured base, the hardener and/or the sealing material are characterized in that they contain at least one photoinitiator which releases and/or constitutes a tertiary amine and/or hydrazine and/or hydrazine, And, released and/or The constituent amine or ruthenium or osmium is catalyzed by hardening by a hardener containing at least one epoxide compound.

The binder and/or sealing material preferably does not contain: - a (meth) acrylate based compound / polymer, - a metal based catalyst, - all other types of polyenes, organic polymers containing double bonds and organic copolymerization Except for decane, such as vinyl decane, propenyl decane and methacryl decane, - ethylene-containing polymer/copolymer, - more than 5% by weight of decane terminated / decane terminated base polymer, - absorption A substance with a strong UV light, such as a pigment that absorbs UV light, such as TiO ₂ .

Depending on the embodiment, the base and/or sealing material may be free of all or a few of the above ingredients and additives.

In the case of this new sealing material system, the hardener is based on epoxides, and in the absence of co-hardening intentions, the hardener is generally free of manganese oxide, inorganic and organic peroxides, vinyl compounds and isocyanates. In particular, in the case where only at least one epoxide compound is used as the hardening agent, the above case is applicable. In the case of co-hardening, it is preferred to use at least one other hardening agent in addition to the at least one epoxide compound, which is selected from the group consisting of manganese oxide, inorganic and organic peroxides, vinyl compounds and isocyanates, and in particular, simultaneously using a ring. Oxides and isocyanates, or epoxides and manganese oxides. These epoxide compounds are preferably added only to the hardener. Thus, the hardening of the sealing material is achieved by at least one epoxide-based compound.

The at least one epoxide-based compound is referred to in the following as "epoxide compound", in part, regardless of whether it is a monomer, oligomer, polymer and/or copolymer. In the present application, the term "epoxide compound" means at least one aliphatic and/or aromatic epoxide compound which is monofunctional and/or polyfunctional and based on monomers, oligomers and/or polymerizations. Things. From this group, at least one such epoxide-based compound is selected. The term "epoxide compound" also generally includes an epoxy group.

All of these epoxide compounds are preferably miscible with each other because they are preferably in a liquid state. Also present in such epoxy resins are epoxy resins which are solid at room temperature which are capable of melting and "dissolving" in the liquid epoxy resin and/or reactive diluent. Epoxides are used as reactants, particularly for the sulfhydryl groups of the base polymer. The intrinsic effect is exerted on the hardening conditions and the mechanical properties of the sealing materials by selecting the (e.g.) epoxide compound.

The hardener contains at least one epoxide-based compound. This epoxide compound is used as a hardener. The hardener preferably contains at least one epoxide compound, wherein the total content of the epoxide-based compound is from 5 to 100, from 30 to 98, from 40 to 95, from 50 to 90, from 60 to 85 or from 70 to 80% by weight. The desired total amount of epoxide compound can be employed herein in the form of a epoxide terminated compound.

Here, the epoxy group of the epoxide compound is chemically reacted with, in particular, the thiol group of the base polymer, and optionally with a small amount of other thiol group-containing compounds such as mercaptopropyltrimethylnonane. In particular, such a compound may be added in an amount of from 0.1 to 5% by weight in the base material or the sealing material to adjust the mechanical properties and adhesion.

Although the functionality of the epoxide compound can in principle be from 2 to 5, mixtures of different functionalities are mostly present. The average functionality of the at least one epoxide compound used as the hardener is preferably from 2.0 to 3.0 or from 2.2 to 2.8. The epoxide compound is preferably at least one aliphatic and/or aromatic epoxide compound, which comprises an average of 2 to 3 independent of each molecule. The epoxy group.

More preferably, the epoxide is in the form of bisphenol A propylene oxide ether, bisphenol F propylene oxide ether, aliphatic polyethylene glycol-propylene oxide ether and/or ethyl carbendazole epoxy derivative. A compound is added to the hardener. Epoxide terminated polythioethers or polythioether sulfides and/or epoxy polysulfides may also be added. Further, it is especially preferred to use at least one epoxy novolac resin which is preferably a crosslinked epoxy novolac resin. The epoxide compound may also be based on a plurality of the above categories, such as bisphenol A/F epoxy resin or bisphenol F novolak resin. So-called "reactive diluents" (epoxy terminated, monofunctional and/or polyfunctional) can be combined with any of the above epoxy resins, for example to adjust viscosity and flexibility. Examples of reactive diluents are 1,4-butanediol-propylene oxide, 2-ethyl-hexyl-glycidyl ether, 1,6-hexanediol propylene oxide ether. In general, all of the epoxy resins can be combined with each other depending on the desired characteristic curve and used as a hardener for the base polymer terminated by the thiol group.

According to a preferred embodiment, the hardening agent of the chemical base has at least one epoxide terminated, endless sulfhydryl-based polysulfide polymer and/or polythioether polymer and/or polysulfide sulfide polymer. It is used as a hardener rather than a base polymer. The polymer is preferably a liquid or high viscosity polymer having, in particular, an epoxy equivalent of from 200 to 800 g/eq.

Wherein the invention surprisingly finds, in particular, epoxide compounds based on epoxy novolac resins, such as DEN 431, DEN 438, DEN 439, and/or based on bisphenol A epoxy resins and/or bisphenol F epoxy resins. Epoxide compounds, such as DER 354, DER 331, are particularly suitable for use in combination with the photoinitiators of the invention under the action of UV light for the hardening of, in particular, mercapto terminated polymers.

The epoxy equivalent of the epoxide compound used as the hardener is preferably 120 to 700 g/eq, particularly preferably from 140 to 400 g/eq, most preferably from 170 to 250 g/eq. In particular, the epoxide-terminated, end-free sulfhydryl-based polysulfide polymer and/or polythioether polymer and/or polysulfide sulfide polymer have an epoxy equivalent weight of from 200 to 800 g/eq.

The epoxide compound is preferably: based on bisphenol A epoxy resin, having an epoxy equivalent of 170 to 200 g/eq; based on bisphenol F resin, having an epoxy equivalent of 150 to 180 g/eq; and, based on epoxy novolac resin The epoxy equivalent is from 160 to 220 g/eq. All epoxy resins can be used depending on the desired characteristics and the specific application.

The following epoxide compounds are best used: 1) bisphenol F epoxy resin, such as DEN 354 (Olin Epoxy), 2) bisphenol A resin, such as DER 336, DER 331 (Olin Epoxy), 3) bisphenol A/F epoxy resin, such as DER 351, DER 324, DER 335 (Olin Epoxy), 4) epoxy novolac resin, such as DEN 431, DEN 438, DEN 439 (Olin Epoxy), 5) based on polysulfide And epoxide terminated prepolymers of polythioethers, such as Thioplast EPS 25 (Akzo Nobel), and 6) alcohol/diol based epoxy terminated reactive diluents, such as 1,4-butyl Glycol propylene oxide ether (DER 731; Olin Epoxy), 2-ethyl-hexyl-propylene oxide (DER 728; Olin Epoxy), C ₁₂ -C ₁₄ - propylene oxide (DER 721; Olin Epoxy)).

Among them, in the case of using an epoxide-terminated compound, it is important that the molar excess of the epoxide compound relative to the 1 Mol reactive SH group is 1.05 to 2 with respect to the total content of the thiol-terminated base polymer. .

The epoxide compound may have an epoxy equivalent weight of from 120 to 700 g/eq, from 140 to 400 g/eq, or from 160 to 250 g/eq.

All of the components of the base polymer of the binder and all of the epoxide-based compounds of the hardener are preferably liquid at room temperature, are highly viscous liquids/slurry, and/or are soluble in organic solvents. Substance. This helps in the uniform mixing of these ingredients.

The hardener may be added with an additive such as decane. However, the hardener preferably does not contain a cycloaliphatic epoxy resin such as hydrogenated bisphenol A propylene oxide ether, hydrogenated bisphenol A propylene oxide ether oligomer, hydrogenated bisphenol F propylene oxide ether, hydrogenation Bisphenol F propylene oxide ether oligomer, and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexyl carboxylate. The hardener may be free or substantially free of water. The hardener typically does not contain a softener.

The binder and/or the sealing material preferably contains at least one additive selected from the group consisting of a photosensitizer, a filler, a lightweight filler, a thixotropic agent, a softener, an adhesion promoter, an antioxidant, a flame retardant, a crosslinking agent, A group consisting of a resin and an organic solvent.

Based on the reaction between the epoxide compound and the thiol group of the base polymer, a network based on hydroxy sulphide and/or hydroxy sulphide sulfide and/or hydroxy sulphide is formed which constitutes the hardened sealing material.

Another solution to achieve the above object of the present invention is a sealing material system and/or sealing material comprising an uncured sulphur-containing polymer-based binder and at least one for the manufacture and hardening of the sealing material. A hardener composition of an epoxide compound, wherein the uncured base contains a base based on a polyether, a polysulfide, a polysulfide, a polysulfide sulfide, a copolymer of the above, and/or a mixture of the foregoing a polymer capable of activating and releasing amine radicals and/or purine free radicals and/or purine free radicals under the action of high-energy actinic radiation, which is capable of Used as a catalyst for hardening after constituting an amine compound or a ruthenium compound or a ruthenium compound, and wherein, from the action of high-energy actinic radiation, self-releasing of amine radicals and/or ruthenium radicals and/or ruthenium radicals, / or from the constituent amine compound and / or bismuth compound and / or bismuth compound, the mixture of the base material and the hardener which together constitute the sealing material can be hardened, and the mixture can be called a sealing material from the start of hardening. . The sealing material system represents a system of uncured base, hardener and sealing material. Therefore, the composition, characteristics, method, and function of the sealing material system are the same as those of the uncured base material, the curing agent, and the sealing material, and thus will not be repeatedly described herein.

Another solution of the invention to achieve the above object is a sulphur-free polymer-based uncured base for the manufacture of sealing materials, in particular for hardening according to the instructions ("on demand"). The uncured base material comprises a thiol-terminated base polymer and a light based on a polyether, a polysulfide, a polysulfide sulfide, a polysulfide, a copolymer thereof and/or a mixture thereof. An initiator, and the photoinitiator is activated by high-energy actinic radiation to form a tertiary amine compound or a ruthenium compound as a catalyst after releasing an amine radical and/or a ruthenium radical and/or a ruthenium radical A ruthenium compound that catalyzes the reaction between a ruthenium terminated base polymer and an epoxide-based hardener.

The uncured sealing material prepared according to the hardening of the instruction ("on demand") is characterized in that the sealing material is a mixture of an uncured base material and a hardener containing at least one epoxide compound, the sealing material. Containing a photoinitiator capable of activating and releasing an amine radical and/or a ruthenium radical and/or a ruthenium radical under the action of high-energy actinic radiation, the radical being used after forming an amine compound or a ruthenium compound or a ruthenium compound As a catalyst for hardening, and from the action of high-energy actinic radiation, from the release of amine radicals and/or hydrazine radicals and/or hydrazine radicals, and from the formation of amine compounds or hydrazine compounds or hydrazine compounds, Sealing material occurs hardening. The hardening of the sealing material is rapidly accelerated from the action of high-energy actinic radiation.

Another solution of the present invention for achieving the above object is a hardener for producing a sulfur-containing polymer-based sealing material, characterized in that the hardener contains at least one epoxide compound and at least one photoinitiator, and At least one photoinitiator capable of being activated by high-energy actinic radiation and capable of releasing and/or constituting an amine and/or rhodium and/or ruthenium, which can be used as a catalyst for epoxide-containing compounds The hardener achieves hardening of the base polymer terminated by the thiol group.

In the case of the sealing material system of the present invention, in the case of the sealing material of the present invention, irradiation with high-energy actinic radiation is initiated to initiate and/or accelerate the hardening of the uncured sealing material.

Another solution of the present invention for achieving the above object is a hardener comprising a sulfur-containing polymer having a backbone based on: 1) polysulfide, 2.) polysulfide, 3.) poly Sulfide sulfide, 4.) a copolymer containing a proportion of polysulfide and/or polysulfide, 5.) a mixture of the above, wherein the polymers are terminated by an epoxide.

Another solution of the invention for achieving the above object is the assembly of the aircraft, which is coated and/or sealed with a sealing material system and/or with the sealing material of the invention and/or by the method of the invention.

The binder and/or sealing material of the present invention may further contain at least one of the following additives, depending on the specific needs: a mixture of a photosensitizer and/or a photoinitiator is preferably used to target the absorption wavelength of the sealing material. Sexual adjustment. The photosensitizer can shift the absorption edge and/or absorption range of the chemical system (a sterically hindered tertiary amine and/or hydrazine and/or hydrazine); in particular, based on hydrated magnesium ruthenate (eg talc), based on hydrogen Alumina (for example Al(OH) ₃ ), feldspar based, quartz powder based and/or filler based on calcium silicate and/or aluminum silicate, particularly preferably at least one filler having a particle size of predominantly 1 to 20 μm. Add fillers to improve mechanical properties. Calcium citrate, hydrated magnesium citrate, aluminum citrate, quartz powder and/or aluminum hydroxide (for example aluminum trihydrate) are fillers suitable for UV irradiation. The fillers having a slightly lower applicability to the binder and sealing material of the present invention are: fillers based on CaCO ₃ , TiO ₂ , carbon black and/or BaSO ₄ , and fillers having significant Fe content and/or containing other heavy metals; Lightweight fillers based on polyurethanes and their copolymers, polyamide waxes and/or polyolefin waxes; lightweight fillers are also used to reduce density. As an alternative or in addition, hollow fillers can also be used; in particular thixotropic agents based on feldspar, decanoic acid, sepiolite and/or bentonite. Thixotropic agents are used to adjust rheological properties, in particular thixotropic properties, for stable application of the sealing material; in particular based on adipates, benzoates, citrates, phthalates and/or terphenyls Softener. Softeners are used to enhance the flexibility of the sealing material. It is often not necessary to use a softener. Epoxy-terminated reactive diluents can also be used to achieve flexibility; adhesion promoters, especially based on phenolic resins, resole resins and/or decane/stanol/hydroxane (referred to herein as "decane") For example, based on organofunctional alkoxydecanes such as mercaptopropyltrimethoxydecane, mercaptopropyltriethoxydecane, glycidoxypropyltrimethoxydecane, glycidoxypropyltriethoxydecane And methacryloxymethyltrimethoxydecane, and/or (methacryloxymethyl)methyldimethoxydecane, and/or di-decyl-decane. Adhesives are used as adhesion promoters to enhance adhesion between the sealing material and the substrate. If an epoxy-carrying adhesion promoter such as glycidoxypropyltrimethoxydecane and glycidoxypropyltriethoxysilane is used, it needs to be applied to the hardener component, otherwise The SH group of the base polymer may react prematurely with these epoxy groups; antioxidants, especially sterically hindered phenols, anilines based and/or as so-called "Hindered Amine Light Stabilisators" (HALS, hindered amine light) Stabilizers), for example, sterically hindered amine based light stabilizers, such as 4,6-di(dodecylthiomethyl)-o-cresol, ethylene-bis(oxyethyl)di-(3- (5-tert-Butyl-4-hydroxy-m-tolyl)-propionate, thiodiethyl-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propyl ester ], pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propyl), and/or aniline, such as N-isopropyl-N'-phenyl-p-phenylene An amine. An antioxidant is used to capture free radicals and/or other separated products produced by the aging process of the polymer matrix and to help slow or prevent aging of the sealing material, such as yellowing or embrittlement; (SH terminated) thiol a binder (such as a derivative of thiol carboxylic acid of Bruno Bock / Thiocure®) which preferably further improves mechanical properties; a flame retardant, in particular based on phosphates, based on ammonium polyphosphate, based on melamine, based on aluminum hydroxide, and Or based on magnesium hydroxide. Flame retardants are used to enhance the fire protection properties of the sealing material, for example to retard the light-off of the sealing material, to spontaneously end the combustion process and/or to reduce the generation of smoke; and/or At least one is especially an organic solvent based on esters and/or ethers, such as ethyl acetate and/or monopropylene glycol monomethyl ether, which contributes to the uniform distribution of the liquid or high viscosity mixture, but usually no solvent is used.

The base composition of the present invention preferably comprises: a base polymer comprising a content of from 30 to 98% by weight, preferably from 40 to 95% by weight, from 45 to 90% by weight, from 50 to 85% by weight, from 55 to 80% by weight or from 60 to 75% by weight. At least one thiol terminated polymer/copolymer, optionally containing from 0 or 0.001 to 20% by weight of monomer And/or an oligomer which comprises from 0 or 0.001 to 10% by weight of the base polymer; optionally at least one softener having a total content of 0% by weight, or 0.1 to 30% by weight, 2 to 20% by weight, 5 Up to 15% by weight, or 6 to 10% by weight; optionally containing at least one filler, the total content being 0% by weight, or 0.1 to 50% by weight, 2 to 40% by weight, 5 to 30% by weight, 10 to 20% by weight, or 6 to 15% by weight Optionally containing at least one light filler having a total content of 0% by weight, or 0.1 to 30% by weight, 3 to 25% by weight, 5 to 20% by weight, or 8 to 15% by weight; optionally containing at least one thixotropic agent, The content is 0% by weight, or 0.01 to 30% by weight, 0.01 to 10% by weight, 0.2 to 25% by weight, 0.5 to 20% by weight, 1 to 15% by weight, 0.5 to 8% by weight, or 1.5 to 5% by weight, wherein in principle more than 10% can also be used. The amount of %, especially in the case where the thixotropic agent is used as a filler at the same time and is sufficiently permeable to high-energy actinic radiation, wherein in this case the content is only included in the thixotropic agent; optionally containing at least one photoinitiator , which is capable of releasing a radical based on a tertiary amine and/or hydrazine and/or hydrazine in a total amount of 0% by weight, or 0.05 to 5% by weight, 0.1 to 4% by weight, 0.3 to 3% by weight, or 0.6 to 2% by weight; The case comprises at least one photosensitizer which is capable of shifting the absorption spectrum of the sealing material formulation to a total content of 0% by weight, or 0.05 to 5% by weight, 0.1 to 4% by weight, 0.3 to 3% by weight, or 0.6 to 2% by weight. Optionally containing at least one adhesion promoter, the total content of which is 0% by weight, or 0.1 to 10% by weight, 0.3 to 8% by weight, 0.6 to 6% by weight, 1 to 5% by weight, 2 to 4% by weight, or 1.5 to 3% by weight; Containing at least one anti-aging agent, the total content of which is 0% by weight, or 0.5 to 2.5 wt%, or 0.5 to 1.5 wt%; optionally containing at least one flame retardant, the total content of which is 0 wt%, or 0.5 to 40 wt%, or 0.5 to 10 wt%; optionally containing at least one mercaptan-based a crosslinking agent (for example, a derivative of a mercaptocarboxylic acid of Bruno Bock/Thiocure®), which preferably further improves mechanical properties, and has a total content of 0% by weight, or 0.1 to 10% by weight, or 0.5 to 6% by weight; and, as the case may be The organic solvent containing at least one ester and/or ether is present in a total amount of 0% by weight, or 0.1 to 15% by weight, or 2 to 10% by weight.

For example, a vacuum dissolver can be used to obtain a homogeneous mixture of the base.

The hardener of the present invention preferably comprises: at least one epoxide compound in a total amount of from 20 to 100, from 30 to 98, from 40 to 95, from 50 to 90, from 60 to 85, or from 70 to 80% by weight; optionally containing at least one a photoinitiator capable of releasing a radical based on a tertiary amine and/or hydrazine and/or hydrazine in a total amount of 0% by weight, or 1 to 90% by weight, 2 to 50% by weight, or 3 to 20% by weight; At least one photosensitizer having a total content of 0% by weight, or 1 to 90% by weight, or 2 to 50% by weight, or 3 to 20% by weight; optionally containing at least one thixotropic agent, the total content being 0% by weight, or 0.01 to 10 wt%, or 0.5 to 5 wt%. Furthermore, the hardener preferably also contains a thixotropic agent based, for example, on pyrolysis, since the thixotropic agent is particularly suitable for adjusting the flow characteristics of the hardener; and, as the case may be, at least one ester and/or ether based The organic solvent has a total content of 0% by weight, or 0.1 to 15% by weight, or 2 to 10% by weight.

For example, a vacuum dissolver can be used to obtain a homogeneous mixture of the hardener.

The sealing material composition of the present invention preferably comprises: at least a content of from 20 to 97% by weight of the base polymer before crosslinking reaction with the epoxide compound-based hardener, preferably at least one thiol terminated polymer 40 to 95 wt%, 45 to 90 wt%, 50 to 85 wt%, 55 to 80 wt% or 60 to 75 wt%; at least one content of 20 to 97 wt%, after crosslinking reaction with an epoxide-based hardener The base polymer, preferably in an amount of 40 to 95% by weight, 45 to 90% by weight, 50 to 85% by weight, 55 to 80% by weight or 60 to 75% by weight, based on the hydroxy sulfide after crosslinking with the epoxide a polymer/copolymer of a hydroxysulfide and/or a hydroxy sulfide sulfide; at least one photoinitiator capable of releasing a radical based on a tertiary amine and/or a ruthenium and/or osmium in an amount of 0.05 to 5 wt% 0.1 to 4 wt%, 0.3 to 3 wt%, or 0.6 to 2 wt%, and/or the total content of the radicals and/or the resulting compound after a short period of time is 0 wt%, or 0.05 to 5 wt%, 0.1 Up to 4 wt%, 0.3 to 3 wt%, or 0.6 to 2 wt%; optionally containing at least one photosensitizer, the total content of which is 0 wt%, or 0.05 Up to 5 wt%, 0.1 to 4 wt%, 0.3 to 3 wt%, or 0.6 to 2 wt%; at least one epoxide compound, the total content of which is 1 to 40, 3 to 30, 5 to 25, 7 to 20, 8 to 18, Or 9 to 16% by weight; optionally containing at least one filler, the total content of which is 0% by weight, or 0.1 to 50% by weight, 2 to 40% by weight, 5 to 30% by weight, 10 to 20% by weight, or 6 to 15% by weight; At least one lightweight filler having a total content of 0% by weight, or 0.1 to 30% by weight, 3 to 25% by weight, 5 to 20% by weight, or 8 to 15% by weight; optionally containing at least one thixotropic agent, the total content of which is 0% by weight , or 0.01 to 30 wt%, 0.01 to 10 wt%, 0.2 to 25 wt%, 0.5 to 20 wt%, 1 to 15 wt%, 0.5 to 8 wt%, or 1.5 to 5 wt%, wherein in principle an amount of more than 10 wt% may also be employed, especially in the The thixotropic agent is used as a filler at the same time and is sufficiently permeable to high-energy actinic radiation, wherein in this case the content is only counted as a thixotropic agent; optionally containing at least one softening agent, the total content of which is 0% by weight, or 0.1 to 30 wt%, 2 to 20 wt%, 5 to 15 wt%, or 6 to 10 wt%; optionally containing at least one adhesion promoter, the total content of which is 0 wt%, or 0.1 to 10 wt%, 0.3 to 8 wt%, 0.6 to 6 wt% %, 1 to 5 wt%, 2 to 4 wt%, or 1.5 to 3 wt%; optionally containing at least one anti-aging agent, the total content of which is 0 wt%, or 0.5 to 2.5 wt%, or 0.5 to 1.5 wt%; The case contains at least one organic solvent based on esters and/or ethers, the total content of which is 0% by weight, or 0.1 to 15% by weight, or 2 to 10% by weight.

For example, a uniform mixture of the sealing material can be obtained using a Techkit cartridge mixer or a static mixer ("Side by Side" or as a "bulk mixer").

The weight of the thiol-terminated base polymer and the epoxide-based compound in the hardener is preferably from 100:3 to 100:50, particularly preferably without taking into account the content of other compounds in the composition. It is 100:4 to 100:25, 100:5 to 100:15, or 100:6 to 100:12.

In the case of the sealing material system of the present invention, the base material is mixed with the hardener in such a manner that the epoxy group of the hardener is superstoichiometrically relative to the base of the base material of the base material during hardening. Wherein, the excess of the epoxy group is preferably from 1 to 80 mol-%, particularly preferably 5 It is up to 50 mol-%, preferably 10 to 30 mol-%.

The weight of the binder and the epoxide-based hardener is preferably from 100:3 to 100:30, and more preferably from 100:4 to 100, taking into account the content of other compounds in the composition. 25,100:5 to 100:15, or 100:6 to 100:12.

The molecular weight of the binder and the epoxide-based hardener is preferably from 0.6:1 to 5:1, particularly preferably from 0.8:1 to 4:1, taking into account other amounts in the composition. 0.9:1 to 3:1, or 1:1 to 2:1.

The weight of the thiol-terminated base polymer and photoinitiator is preferably from 100:0.1 to 100:5, and more preferably from 100:0.5 to 100:4,100, without taking into account other amounts in the composition. : 0.8 to 100:3, or 100:1 to 100:2.

The molecular weight of the sulfhydryl group and the epoxy group is preferably from 1:0.8 to 1:2, and more preferably from 1:0.9 to 1:1.5, 1:0.95, without taking into account other contents and groups in the composition. To 1:1.3, or 1:0.98 to 1:1.2.

The sealing material of the present invention and the sealing material system of the present invention preferably have at least one thiol terminated base polymer based on polyether, polythioether, polysulfide sulfide, polysulfide, copolymer thereof and/or mixtures thereof At least one photoinitiator based on a sterically hindered tertiary amine and/or sterically hindered and/or sterically hindered oxime, at least one epoxide compound, and optionally at least one additive. Preferably, the at least one additive may be selected from the group consisting of a photosensitizer, a filler, a lightweight filler, a thixotropic agent, a softener, an adhesion promoter, an antioxidant, a flame retardant, a crosslinking agent, and a resin. And organic solvents. It is preferred to contain hydrated magnesium niobate, aluminum niobate, aluminum hydroxide (for example, aluminum trihydrate) and/or calcium niobate as a filler. A portion of these primary components, as well as a portion of such additives, may also be included in the binder and/or the hardener.

The material of the present invention preferably has the following characteristics: The base material and sealing material of the present invention generally have all or most of the following characteristics: measured according to a Brookfield viscometer at 23 ° C by spindle 7 at 2 to 10 rpm. The dynamic viscosity of the base material and the sealing material according to DIN 65262-1 of the invention is preferably from 1 to 2500 Pa. s, or 10 to 1800 Pa. s.

Preferably, depending on the specific layer thickness and/or UV source, UV irradiation is carried out for a period of from 1 s to 5 min, preferably from 5 s to 3 min or from 10 s to 1 min. After the UV irradiation, the non-stick time of the sealing material determined according to DIN 65262-1 is preferably from 1 s to 10 min (especially depending on the thickness of the layer), and is usually from 0.3 to 5 min or from 1 to 3 min.

The treatment time of the uncured sealing material according to DIN 65262-1 is preferably from 0.5 to 24 hours (depending on the amount of photoinitiator used for the substrate to be irradiated), particularly preferably from 0.5 to 6 or from 0.5 to 2 hour.

According to DIN 65262-1, the non-stick time of the sealing material produced by the method of the invention after high-energy actinic irradiation is from 0.05 to 10 minutes, in particular also depending on the concentration of the photoinitiator.

Preferably, the sealing material of the present invention has a complete hardening time determined according to ISO 7619-1, or a time for achieving a Shore A hardness of 30, of 1 to 960 min, preferably 5 to 300 min, and more preferably 10 to 90 min, depending on the amount of photoinitiator and/or layer thickness.

The density of the base material and sealing material of the present invention determined according to ISO 2781 is preferably from 0.9 to 1.6 g/cm ³ and usually from 1.0 to 1.5 g/cm ³ .

According to the 2 weeks after the implementation of UV irradiation, at 23 ± 2 ° C and 50 ± 5% relative The Shore A hardness determined according to ISO 7619-1 of the sealing material of the present invention is preferably from 20 to 80, particularly preferably from 30 to 60, more preferably from 40 to 55, measured by exposure to air at atmospheric humidity. .

According to the measurement performed when exposed to air at 23±2° C. and 50±5% relative air humidity after 2 weeks of UV irradiation, the elongation at break of the sealing material of the present invention determined according to ISO 37 is 100. Up to 1000%, especially 200 to 800% or 300 to 600%.

The elongation at break of the sealing material of the present invention determined according to ISO 37 is preferably from 100 to 800%, particularly preferably from 200 to 600%, based on the measurement after 168 hours of fuel storage with the fuel type Jet A1 at 60 ° C. 300 to 500%.

The elongation at break of the sealing material of the present invention determined according to ISO 37 is preferably from 100 to 700%, particularly preferably from 200 to 600%, based on the measurement after 300 hours of fuel storage with the fuel type Jet A1 at 100 ° C or 300 to 500%.

The breaking elongation of the sealing material of the present invention determined according to ISO 37 is preferably from 100 to 700%, particularly preferably from 200 to 500% or from 250 to 350%, based on the measurement after storage in water at 35 ° C for 1000 hours.

The peel strength of the sealing material of the present invention on aluminum alloy 2024 T3 determined according to DIN 65262-1 is preferably from 60 to 350 N/25 mm, particularly preferably from 100 to 250 N/25 mm or from 150 to 200 N/25 mm.

The peeling strength of the sealing material of the invention according to DIN 65262-1 is preferably from 50 to 350 N/25 mm, more preferably from 100 to 300 N/25 mm or from 150 to 200 N/25 mm, such as solvents. the base paints, such as epoxy paint 37035A (Akzo Nobel Aerospace Coatings company); for example, based on the aqueous epoxide-based paint, such as Seevenax ^® 313-01 and Seevenax ^® 313-02 (Mankiewicz Inc.); lacquer coating, for example based on Aqueous paints for epoxies such as Seevenax ^® 311-03 (Mankiewicz); topcoat F 70-A (Mapaero); and/or polyurethane-based solvent-based paints such as Aerodur ^® C21-100 (Akzo Nobel) and Alexit ^® 406-22 (Mankiewicz).

The tensile strength of the sealing material of the present invention determined according to ISO 37 is preferably measured according to the measurement performed after exposure to air at 23 ± 2 ° C and 50 ± 5% relative air humidity after 2 weeks of UV irradiation. It is from 0.5 to 3.8 MPa, particularly preferably from 1 to 3.5 MPa or from 1.8 to 3.0 MPa.

The tensile strength of the sealing material of the present invention determined according to ISO 37 is preferably from 0.5 to 3.5 MPa, particularly preferably from 1 to 3.0 MPa, based on the measurement after 168 hours of fuel storage with fuel type Jet A1 at 60 ° C. 1.5 to 2.8 MPa.

The tensile strength of the sealing material of the present invention determined according to ISO 37 is preferably from 0.5 to 3.5 MPa, particularly preferably from 1 to 3.0 MPa, based on the measurement after 300 hours of fuel storage with the fuel type Jet A1 at 100 ° C. 1.2 to 2.8 MPa.

The tensile strength of the sealing material of the present invention determined according to ISO 37 is preferably from 0.5 to 3.5 MPa, particularly preferably from 1 to 3.0 MPa or from 1.5 to 2.7 MPa, based on the measurement after storage in water at 35 ° C for 1000 hours.

The sealing material system of the present invention and/or the sealing material of the present invention preferably has a Shore A hardness of at least 10 (measured after 5 to 600 minutes from the completion of high-energy actinic irradiation), and a Shore of 30 to 60 Hardness A (measured after 2 weeks from the completion of high-energy actinic irradiation).

And/or in terms of low temperature flexibility of the sealing material of the present invention, for detection, after high energy actinic irradiation, at room temperature of 23 ± 2 ° C and relative humidity of 50 ± 5% The film-like sealing material is stored for 2 weeks, and then briefly cooled to a temperature of -55 ± 2 ° C, at which the sealing material is bent by 30°, followed by defects at room temperature according to internal test specifications. Conduct a visual inspection. Accordingly, the sealing material of the present invention preferably does not exhibit cracks and other defects caused by bending at a low temperature.

After complete hardening, the sealing material system of the present invention and/or the sealing material of the present invention preferably has the following characteristics: the sealing material has no cracks or other defects, and the defects are determined at -55 when determining low temperature flexibility. Produced by bending at 30 °C at a temperature of ±2 °C, after 168 hours of fuel storage at 60 °C, 300 hours after fuel storage at 100 °C, and 1000 hours after storage at 35 °C, the tensile strength is 0.5 to 3.8 MPa, after storage of the fuel at 60 ° C for 168 hours, after 300 hours of fuel storage at 100 ° C, and after storage for 1000 hours at 35 ° C, the elongation at break is 100 to 800%, and / Or the density is 1.00 to 1.50 g/cm ³ .

After complete hardening, the sealing material system of the present invention and/or the sealing material of the present invention preferably has the following characteristics: tensile strength of 0.5 to 3.5 MPa, elongation at break of 100 to 900%, and/or peel strength of 50. Up to 300N/25mm.

In particular, it is here on a substrate composed of aluminum or an aluminum alloy, titanium or titanium alloy, stainless steel, a composite material (for example, carbon fiber reinforced plastic CFK), and/or on a painted substrate (for example, coated with at least a solvent-containing or aqueous base paint and/or paint, which is based in particular on The peel strength is determined by epoxy lacquer, polyester lacquer or polyurethane lacquer.

Other surprising advantages are enumerated below: surprisingly, under high-energy actinic illumination, for example in the case of exposing the sealing material mixture of the invention to UV, the release of the tertiary amine and/or The photoinitiator of rhodium and/or rhodium also triggers and/or accelerates the chemical reaction of the epoxy compound with the mercaptan.

The present inventors have surprisingly discovered that a photoinitiator that releases a small amount of tertiary amine free radicals, hydrazine free radicals and/or hydrazine free radicals provides a sufficient amount of catalytic activity for the hardening of the binder.

The present inventors have unexpectedly discovered that such a small amount (e.g., 0.1 wt%) of photoinitiator in the sealing material is sufficient to effect catalytic activation for the masking portion, the back card portion, and the borehole.

The invention has surprisingly found that the sealing material system of the invention achieves both a greater layer thickness (e.g., a layer thickness of about 7 mm) and an accelerated hardening for such layer thicknesses.

This type of sealing material, which is extremely fast and has a long process time, is clearly revealed for the first time.

This type of sealing material, which is extremely hard to harden and even works according to the instructions ("on demand"), is clearly revealed for the first time.

Surprisingly, a very short non-stick time is achieved at a given processing time and a very short total hardening time is achieved compared to the prior art.

The present inventors have surprisingly found that the sealing material of the present invention begins to harden by a very small UV dose, i.e., by a UV dose of from about 1 J/cm ² .

When the method of the invention is used, it is possible to harden, for example, an extremely thin sealing material layer of, for example, 0.1 to 0.5 μm, and an extremely thick sealing material layer of 3 to 7 mm by UV light, so that it can be used for 0.1 to 7 mm. The range is hardened. Wherein, the sealing materials are both planar and Can be applied in strips.

The coating process of the present invention is particularly suitable for use in the aerospace industry, but is also applicable to any situation where it is desirable and/or preferably achieves faster hardening and predominantly extremely fast surface hardening over a relatively long processing time.

The coating method of the present invention is particularly suitable for: sealing structural elements (such as fuel tanks) and areas to be sealed (such as stone pavements in gas stations and chemical facilities); structural elements that overlap each other (eg, sheets, Bonding of the film and other substrates; filling of the cavity and the intermediate cavity; in particular coating of metallic materials and composites (eg carbon fiber reinforced or glass fiber reinforced plastic); aerodynamic smoothing and sealing, and for example In the area of the borehole, corrosion protection is achieved on the damaged or removed parts of the metal component. For example, during transportation, the method can also implement a carrying function.

The method of the invention is particularly suitable for use in the transportation industry, for example in automotive manufacturing, rail vehicle manufacturing, shipbuilding, aircraft manufacturing or spacecraft manufacturing, instrumentation and machinery manufacturing, construction, or for furniture manufacturing.

The sealing material system of the invention, the base material of the invention, the hardener of the invention and/or the sealing material of the invention are particularly suitable for the manufacture and maintenance of aircraft and spacecraft, the manufacture and maintenance of automobiles and rail vehicles, shipbuilding, instruments And machinery manufacturing, construction (for example, sealing the floor in gas stations and chemical facilities), as a casting resin, or for the manufacture of casting resins for electrical engineering and electronics.

Examples and comparison examples

The subject matter of the present invention is further described below in conjunction with a number of embodiments.

General Manufacturing and Test Specifications for Sealing Materials of the Invention: The base material of the present invention is manufactured in a vacuum of <50 mbar at a speed of about 2000 rpm in the case of cooling the planetary dissolver with cooling water. First, polymerizing polysulfide polymers (such as Thiokol ^® LP 12, Thioplast ^® G 10 and / or Thioplast ^® G131) and / or polythioether polymers and / or polysulfide sulfide polymers and / or polyethers a photoinitiator based on at least one sterically hindered tertiary amine and/or ruthenium and/or osmium, at least one photosensitizer based on benzophenone and/or isopropyl thioxanthone, for example based on a sea bubble The stone thixotropic agent, and a co-binder based on, for example, a phenolic resin or an organofunctional alkoxysilane, is mixed for 10 minutes. The remaining fillers, for example based on hydrated magnesium ruthenate, aluminum citrate, calcium citrate, polyamine and/or polyethylene wax, and a phosphate-based antioxidant are added, under a vacuum of <50 mbar. The planetary dissolver was further dispersed for about 10 to 20 minutes at a speed of about 2000 rpm. The polysulfides, polythioethers, polysulfide sulfides, polyethers and copolymers thereof are always terminated by sulfhydryl groups.

In order to achieve good dispersion of the base material, it is particularly suitable to use a rotational speed range of 1800 to 2200 rpm and a time of 30 to 40 minutes depending on the composition, rheological properties and instrumentation.

The hardener of the present invention is produced by the epoxide compound and the pyrolysis-based thixotropic agent Aerosil ^® R202 by a planetary dissolver at a speed of about 2000 rpm under a vacuum of <50 mbar. mixing.

To seal, fill and/or coat the structural components and to produce a test body, the binder is mixed with the hardener at a mixing ratio of 100:5 to 100:7, followed by activation with high energy actinic radiation. The sealing material of the invention also hardens without high-energy actinic radiation According to the layer thickness, in the case where the layer thickness is 0.2 to 6 mm, the time required for complete hardening is 24 to 168 hours.

After the sealing material is stored in the air for 7 days under the ambient air temperature of 23 ° C and 50% relative humidity, the mechanical properties of the sealing material, such as the Shore A hardness according to ISO 7619-1 and the ISO according to ISO The tensile strength and elongation at break of 37 were measured. Wherein, after the base material is mixed with the hardener in a manner of being exposed to air, the sealing material is applied to the substrate immediately, and then the sealing material is directly irradiated with high-energy actinic radiation. It is then stored as exposed to air.

To activate the sealing material, a UV planar radiator comprising a Fe-doped Hg lamp with a power of 400 W is typically employed. Here, all commercially available UV light sources, including diodes that emit UV light, and fluorescent or electron beam sources for hardening the actinically activated coating are suitable. The sealing materials are capable of hardening in the wavelength range of 315 to 600 nm, such as UVA and/or UV/VIS.

The formulations of several examples of the invention listed in Table 4 are used to: influence the processing characteristics of three different photoinitiators on the uncured base and the hardened sealing material, and the mechanical properties of the sealing materials. The effect is measured. As with all other examples, the binder and hardener compositions of the present invention were made in accordance with the above specifications. The two sub-mixtures were uniformly mixed at a mass ratio of 100:5, and applied to the aluminum alloy sheet by a self-mixer cavity extrusion at a thickness of 2 mm at about 23 ° C, followed by a Fe-doped UV. The planar radiator was irradiated with a UV dose of 10 J/cm ² , a UV intensity of 0.3 W/cm ² and a distance of 10 cm in a wavelength range of 300 to 600 nm for 40 s. Here, the coating in the hardening is slightly heated, wherein it does not reach 60 °C.

Subsequently, before determining mechanical properties such as hardness, elongation and tensile strength, The hardened sealing materials were removed from the test mold and stored for 7 days at 23 ± 2 ° C and 50 ± 5% relative air humidity by exposure to air. After exposure to air storage, it is then stored in a different medium, see Table 7.

2-Dimethylamino-2-(4-methyl-benzyl)-1-(4-4morpholinyl-phenyl)-butan-1-one was used as the photoinitiator 1. 2-Benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone was used as the photoinitiator 2. A sterically hindered DBN was used as the photoinitiator 3. Triethylene glycol diamine is used as an additional catalyst. It will have an epoxy equivalent of 180-195g/eq and a viscosity of 10-15Pa. A mixture of s bisphenol A epoxy resin (commercially available Epikote 828 or DER 331) and a reactive diluent based on 1,4-butanediol propylene oxide ether is used as a hardener. The mixing ratio of bisphenol A epoxy resin/reactive diluent was 4:1. The properties of the measured examples are listed in Table 5.

Comparative Example 1 (VB1) contained no photoinitiator which was used for a better comparison of the effects of each photoinitiator. Comparative Examples 2 and 3 (VB2 and VB3) contain a sterically hindered tertiary amine as a photoinitiator, but after activation with UV light, the sterically hindered tertiary amine is too low in alkalinity to initiate and/or accelerate The hardening reaction. Therefore, there is no advantage compared with VB1. Surprisingly, the reaction in Example 1 (B1) was significantly accelerated by the use of a sterically hindered DBN. Accordingly, the sterically hindered DBN appears to have a sufficiently high basicity to catalyze the reaction between the SH group and the epoxy group.

In the following Example 2 (B2) and Comparative Example 4 (VB4), the formulation of the present invention was compared with a commercially available conventional manganese dioxide hardening type sealing material MC-780 B-1/2. Activate B2 with UV light once and activate it without UV light. Table 6 shows the composition of these formulations. Table 7 summarizes the characteristics of these sealing materials. It is apparent here that the two sealing materials have the same processing time. Surprisingly, compared with MC-780 B-1/2, the sealing material of the present invention enters a non-stick state and reaches the initial hard state when activated by UV light in advance. The speed of Shore A (Shore A) 30 is significantly accelerated. The sealing material still reaches its final properties without being activated by UV light in advance, but the time elapses is greatly increased. The sealing material of the present invention unexpectedly exhibits good mechanical properties even after being stored in a different medium at a high temperature, for example, at 35 ° C in water, or after being stored in a fuel at 60 ° C or 100 ° C.

When using the sealing material of the present invention, there may be no other non-sterically hindered catalyst in the formulation, see Examples 6 and 7 (B3 and B4). Table 8 describes the composition of these examples, and Table 9 reveals the measured characteristics. It is apparent here that in the absence of the other sterically hindered catalyst, the hardening of the sealing material is greatly reduced.

Overall, despite the significant reduction in hardening, the advanced characteristics of conventional aircraft sealing materials, such as high resistance to various media (eg, fuel resistance at 60 ° C measured after 168 hours), and Water resistance at 35 ° C measured after 1000 hours), resistance to hydraulic fluid, condensed water, deicing fluid, high heat resistance, high temperature flexibility, high weather resistance, for different substrates Higher peel strength, higher elongation at break and higher tensile strength.

Claims (23)

A sealing material for coating a substrate, characterized in that it is a mixture of a substantially uncured base material and a hardener containing at least one epoxide compound, the base material comprising polyether, polysulfide, polysulfide a thiol-terminated base polymer of an ether sulfide, a polysulfide, a copolymer of the above and/or a mixture thereof, the base, the hardener or both containing at least one sterically hindered nitrogen-containing organic base-based photoinitiator And the at least one photoinitiator separates at least one radical based on the nitrogen-containing organic base for each molecule under the action of high-energy actinic radiation, thereby constituting a nitrogen having a pKs value of 6 to 30 of a conjugate acid An organic base which acts as an activating catalyst for the hardening of the binder. The sealing material of claim 1, characterized in that the non-sticking time of the sealing material according to DIN 65262-1 is 0.01 to 10 minutes after the start of high-energy actinic irradiation. The sealing material of claim 1 or 2, wherein the base material is substantially based on at least one liquid polysulfide compound, the molecular end of which carries a sulfhydryl group, respectively, and optionally contains up to about 50 mol-% of disulfide in the molecule. Base (polysulfide sulfide). The sealing material of claim 3, characterized in that, in addition to the at least one liquid polythioether compound, the binder contains at least one disulfide-containing compound in an amount of up to 80% by weight of the binder. A sealing material according to any of the preceding claims, characterized in that the following mercapto terminated polysulfide polymer and/or mercapto terminated polythioether and/or mercapto terminated polysulfide sulfide are used as base polymerization Matter: it contains molecular weight, especially 2500 to 6000g/mol, especially A long-chain polymer preferably having a molecular weight of from 3,300 to 5,000 g/mol also contains a short-chain polymer having a molecular weight of, in particular, from 500 to 2,500 g/mol, particularly preferably from 800 to 1,500 g/mol, wherein the long-chain polymers are short The proportion of chain polymer is preferably from 25:1 to 0.5:1, from 20:1 to 2:1, or from 14:1 to 8:1. A sealing material according to any one of the preceding claims, characterized in that the thiol content of the reactive SH group of the base polymer relative to the entire base polymer is from 0.5 to 10% by weight, from 0.8 to 8% by weight or from 1.2 to 7% by weight. %, the base polymer has a total sulfur content of 1 to 50 wt%, 5 to 45 wt% or 12 to 36 wt%, and as a reactive end group of a mercapto group per molecule, the average functionality of the base polymer is 1.5. To 2.5 or 1.9 to 2.2. A sealing material according to any one of the preceding claims, wherein the at least one epoxide compound is an epoxy novolac resin based on bisphenol A epoxy resin and/or epoxy based on bisphenol F epoxy resin. Compound. The sealing material of claim 7, characterized in that the at least one epoxide compound is based on a bisphenol A epoxy resin having an epoxy equivalent of from 170 to 200 g/eq, based on bisphenol having an epoxy equivalent of from 150 to 180 g/eq. F resin, and/or epoxy novolac resin based on an epoxy equivalent of 160 to 220 g/eq. The sealing material according to any one of the preceding claims, wherein the at least one epoxide compound contains 1,4-butanediol-propylene oxide, 2-ethyl-hexyl-glycidyl ether and/or 1 , 6-hexanediol dioxypropylene ether (reactive diluent). A sealing material according to any of the preceding claims, characterized in that the molar excess of the epoxide compound relative to the 1 Mol reactive SH group is from 1.05 to 2, relative to the total content of the thiol terminated base polymer. The sealing material according to any one of the preceding claims, characterized in that the conjugated acid of the nitrogen-containing organic base used as an activation catalyst for hardening of the binder has a pKs value of from 7 to 28, preferably from 8 to 26. It is especially good for 9 to 20, and most preferably 10 to 15. A sealing material according to any one of the preceding claims, wherein the at least one photoinitiator is a sterically hindered tertiary amine, a hindered ruthenium and/or a sterically hindered ruthenium. The sealing material of claim 12, characterized in that a certain amount of the at least one photoinitiator is added, and the ratio of the tertiary amine and/or cerium and/or cerium compound corresponding to the sealing material is 0.05 to 5 wt%, preferably 0.1 to 4 wt%, particularly preferably 1 to 3 wt%. The sealing material of claim 12 or 13, wherein the at least one photoinitiator is a photolatent 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), photolatent 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), photolatent TMG (tetramethylguanidine), and/or photolatent triethylenediamine (1,4- Diazabicyclo[2.2.2]octane). A sealing material according to any one of the preceding claims, characterized in that the sealing material contains another free catalyst for deep hardening, preferably a free nitrogen-containing organic compound having a pKs value of 6 to 30 of a conjugate acid. A base, particularly preferably a free tertiary amine and/or a free hydrazine and/or a free hydrazine. The sealing material of claim 15 characterized in that the free catalyst is 1,4-dimethylpiperazine, N-methylmorpholine, 2,2'-dimorpholinyldiethyl ether, three ( Methylaminomethyl-phenol), triethylenediamine and/or TMG are preferably triethylenediamine and/or TMG. A sealing material according to any one of the preceding claims, wherein the sealing material contains a photosensitizer to specifically adjust the absorption wavelength of the sealing material. A method of coating a substrate with a sealing material, characterized in that A sealing material coats the substrate, irradiates the sealing material with high-energy actinic radiation, and then hardens the sealing material. The method of claim 18, wherein the high-energy actinic radiation has a wavelength of 315 to 600 nm. The method according to any one of claims 18 or 19, characterized in that the hardening is carried out at room temperature or at a temperature of from 10 to 40 ° C, preferably from 15 to 30 ° C. The assembly of the aircraft is sealed with a sealing material as claimed in any one of claims 1 to 17. An application of the sealing material according to any one of claims 1 to 17 for the manufacture and maintenance of aircraft and spacecraft, the manufacture and maintenance of automobiles and rail vehicles, shipbuilding, instrumentation and machinery manufacturing, construction, and casting Resin, or used in the manufacture of casting resins for the electrical engineering and electronics industries. A method according to any one of claims 18 to 20 for use in the transportation industry for automotive manufacturing, rail vehicle manufacturing, shipbuilding, aircraft manufacturing or spacecraft manufacturing, instrument and machine building, construction, or for furniture Manufacturing.